JP2788391B2 - Lactone ring-opening polymer having phenolic terminal group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel lactone ring-opening polymer. More specifically, the present invention relates to a lactone ring-opening polymer having a phenolic hydroxyl group at a terminal.

[0002]

2. Description of the Related Art Hitherto, various studies have been made on the polymerization of lactones using a non-catalytic method or a catalytic method. It is also known to copolymerize with other lactones (for example, JP-B-39-20521 and JP-B-39-26003).

[0003] Polycaprolactone is useful as a polymer modifier, and is used by being mixed with various thermoplastic resins. For example, it is known to improve moldability (melt fluidity) by mixing polycaprolactone with a polycarbonate resin. However, there is a problem in compatibility between polycaprolactone and a polycarbonate resin, and physical properties and optical characteristics are deteriorated, so that it is not applicable depending on the use.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned compatibility problem by providing a lactone ring-opening polymer having a reactive phenolic terminal group capable of reacting with and binding to a thermoplastic resin. It is to provide coalescence.

The present inventor has sought to achieve the above object,
As a result of intensive research on the method of providing a lactone with a phenolic terminal group, it was found that a lactone ring-opened polymer having a phenolic terminal group can be obtained by reacting a lactone with an alcohol having a specific structure. Was. The present invention has been completed based on this finding.

[0006]

The present invention provides a compound represented by the following general formula [1]:

[0007]

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Wherein R is an aliphatic hydrocarbon group which may contain an ether group having 1 to 10 carbon atoms, R 'is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, m is an integer of 4 to 20, n is an integer of 1 to 100, and p is an integer of 0 to 4. And a lactone ring-opening polymer having a phenolic terminal group.

The lactone ring-opening polymer having a phenolic terminal group of the present invention can be prepared by mixing a substituted or unsubstituted hydroxyaralkyl alcohol and a lactone at an appropriate ratio and heating in the presence of a catalyst to react the alcohol group with the lactone. And the lactone is produced by a ring-opening polymerization reaction, and the degree of polymerization of the lactone can be arbitrarily controlled by adjusting the molar ratio between the lactone and the hydroxyaralkyl alcohol. If the degree of polymerization of the lactone is too high, the reactivity of the phenolic terminal group will decrease, so that the degree of polymerization of the lactone is preferably from 1 to 100.

The hydroxyaralkyl alcohol used here includes, for example, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-bromo-5-hydroxybenzyl alcohol, 3-chloro-4-hydroxybenzyl Alcohol, 3-hydroxy-α-methylbenzyl alcohol, 4-hydroxy-α-methylbenzyl alcohol, 2- (2-hydroxyphenyl) ethanol,
2- (4-hydroxyphenyl) ethanol, 2-methyl-4-hydroxyphenylbenzyl alcohol, 2-
Methyl-6-hydroxyphenylbenzyl alcohol,
2-hydroxy-3-methylphenylbenzyl alcohol, 2-hydroxy-5-methylphenylbenzyl alcohol, 1- (4-hydroxyphenyl) propanol-2, 3- (2-hydroxyphenyl) propanol,
3- (3-hydroxyphenyl) propanol, 2-hydroxy-5-ethylbenzyl alcohol, 3-methyl-4-hydroxyphenyl-α-methylbenzyl alcohol, 4- (2-hydroxyphenyl) butanol-
2,3- (2-hydroxy-5-methylphenyl) propanol, 5- (2-hydroxyphenyl) pentanol, 4- (2-methyl-4-hydroxyphenyl) butanol-2,4- (3-methyl- 4-hydroxyphenyl) butanol-2, 3- (2-hydroxy-4-methylphenyl) butanol, 6- (4-hydroxyphenyl) hexanol-2, 4- (4-hydroxyphenyl) hexanol-3 and the like. .

Lactone is a lactone having 5 to 21 carbon atoms, and the carbon atoms forming the lactone ring may be substituted with a lower alkyl group. Such lactones include, for example, δ-valerolactone, ε-caprolactone,
7-hydroxyheptanoic acid lactone, 8-hydroxyoctanoic acid lactone, 13-hydroxytridecanoic acid lactone, 15-hydroxypentadecanoic acid lactone, 17
-Hydroxyheptadecanoic acid lactone and the like, and these may be used alone or in combination of two or more.

As the catalyst, for example, a known catalyst of an organometallic compound such as lithium, sodium, potassium, aluminum, magnesium, beryllium, zinc, cadmium, boron, or a known Lewis acid catalyst can be used. The amount of the catalyst used is usually 0.001 to 10% by weight, preferably 0.01% by weight, based on the total weight of the lactone used in the reaction.
３3% by weight.

The reaction of the substituted or unsubstituted hydroxyaralkyl alcohol with the lactone is carried out in an inert gas, usually in the presence of a bulky or catalytically inert solvent. As the solvent, for example, benzene, toluene, xylene, ether, benzene, tetrahydrofuran, dioxane and the like are used. The reaction temperature is usually 100 to 200 ° C.
20-180 ° C is preferred. A reaction time of usually several minutes to several tens hours is sufficient. After completion of the reaction, when a solvent is used, the solution is purified by washing with water, and then the solvent is distilled off to obtain a product.

The thus obtained lactone ring-opening polymer having a phenolic terminal group of the present invention can be modified, for example, by binding to the terminal of another thermoplastic resin by utilizing the reactivity of the terminal phenol group. . Examples of such a thermoplastic resin include a polycarbonate resin, a polyester resin, a polysulfone resin, and a polyarylate resin.

[0015]

The present invention will be further described with reference to the following examples. In the examples, parts and% are parts by weight and% by weight, respectively. The acid value and the hydroxyl value were measured in accordance with the Oil and Fat Test Method of the Japanese Pharmacopoeia, and the NMR measurement was carried out with a heavy chloroform solution.

[0016]

EXAMPLE 1 248 parts of m-hydroxybenzyl alcohol and 0.02 part of tetraisopropyl titanate were placed in a reactor having a dried thermometer, stirrer and reflux condenser, and heated to 145 ° C. in a nitrogen stream. And 1140 parts of ε-caprolactone mixed with 0.08 part of tetraisopropyl titanate was added over 70 minutes. During this addition, the temperature gradually increased to 180 ° C. Stirring was continued at 170 ° C. for another 120 minutes to complete the reaction. The resulting reaction product has a hydroxyl value of 75.8 mg KOH / g and an acid value of 2.3.
mg KOH / g, yield was almost quantitative. The NMR chart of this reaction product is shown in FIG. According to this NMR chart, the reaction product was found to be phenol-terminated polylactone (n
= 5).

[0017]

Example 2 The reaction was carried out in the same manner as in Example 1 except that the amount of m-hydroxybenzyl alcohol used was changed to 54 parts. The resulting reaction product had a hydroxyl value of 24.3 mg KOH /
g and acid value were 1.0 mg KOH / g. The yield was almost quantitative. The NMR chart of this reaction product is shown in FIG. From the NMR chart, it can be seen that the reaction product is a phenol-terminated polylactone (n = 20).

[0018]

The lactone ring-opening polymer having a phenolic terminal group of the present invention can be reacted with the terminal of various polymers and bonded thereto, and is therefore extremely useful as a polymer modifier.

[Brief description of the drawings]

FIG. 1 is an NMR chart of a phenol-terminated polylactone produced in Example 1.

FIG. 2 is an NMR chart of a phenol-terminated polylactone produced in Example 2.

Claims (1)

(57) [Claims] [Claim 1] The following general formula [1] [In the formula, R is an aliphatic hydrocarbon group which may contain an ether group having 1 to 10 carbon atoms, and R ′ is 1 to 3 carbon atoms.
10 aliphatic hydrocarbon groups or halogen atoms, m is 4 to 2
An integer of 0, n is an integer of 1 to 100, and p is an integer of 0 to 4. And a lactone ring-opening polymer having a phenolic terminal group.